Interfacial ion transfers between a monolayer phase of cationic Au nanoparticles and contacting organic solvent.

The highly cationic nanoparticle [Au(225)(TEA-thiolate(+))(22)(SC6Fc)(9)] adsorbs so strongly on Pt electrodes from CH(3)CN/Bu(4)NClO(4) electrolyte solutions that films comprised of 1-2 monolayers of nanoparticles can be transferred to nanoparticle-free electrolyte solutions without desorption and ferrocene voltammetry stably observed. (TEA-thiolate(+) = -S(CH(2))(11)N(CH(2)CH(3))(3)(+); SC6Fc = S(CH(2))(6)-ferrocene; Fc = ferrocene). The Fc(+/0) redox couple's voltammetry is used to detect the adsorption. The apparent formal potential (E(o)'(APP)) of the Fc(+/0) couple depends on the electrolyte--its anion, cation, and concentration--in the contacting nanoparticle-free solution. A 10-fold change in electrolyte concentration shifts the Fc(+/0) E(o)'(APP) by 48-67 mV, depending on the electrolyte. The dependency is interpreted to reflect the energetics of transfer of charge-compensating anions from the electrolyte solution to the monolayer nanoparticle "phase", promoted by the formation of Fc(+) sites in the nanoparticle film. This interpretation is supported by electrochemical quartz crystal microbalance results. Some further aspects of the results suggest adsorption of electrolyte cations at the nanoparticle film/electrolyte solution interface. The interface mimics a liquid/liquid interface between immiscible electrolyte solutions, in which the ion transfer approaches permselective behavior. The experimental results show that even 1-2 monolayers of highly ionic nanoparticles can behave as a polyelectrolyte "phase".

Electrospray ionization mass spectrometry of intrinsically cationized nanoparticles, [Au(144/146)(SC(11)H(22)N(CH(2)CH(3))(3)(+))(x)(S(CH(2))(5)CH(3))(y)](x+).

Electrospray ionization triple-quadrupole mass spectrometry of ca. 1.6 nm diameter thiolate-protected gold nanoparticles has been achieved at higher resolution than in previous reports. The results reveal the presence of nanoparticles with formulas Au(144)L(60) and Au(146)L(59), present in the sample as a mixture. The improved resolution is based on lowering m/z by exchanging multiple [-SC(11)H(22)N(CH(2)CH(3))(3)(+)] ligands into the original [-S(CH(2))(5)CH(3)] ligand shell. The nanoparticles are thus intrinsically cationized and appear as a series of 10+ to 15+ mass spectral peaks. The assigned state of charge was confirmed by a collision-induced dissociation measurement.

Ferrocenated au nanoparticle monolayer adsorption on self-assembled monolayer-coated electrodes.

The robust, irreversible adsorption of omega-ferrocene hexanethiolate-protected gold nanoparticles (composition ca. {Au(225)(SC6Fc)(43)}) on electrodes provides an opportunity to investigate their submonolayer and monolayer films in nanoparticle-free solutions. Observations of nanoparticle adsorption on unmodified electrodes are extended here to Au electrodes having more explicitly controlled surfaces, namely self-assembled monolayers (SAMs) of alkanethiolates with omega-sulfonate, carboxylate, and methyl termini, and in different Bu(4)N(+)X(-) electrolyte (X(-) = C(7)H(7)SO(3)(-), ClO(4)(-), CF(3)SO(3)(-), PF(6)(-), NO(3)(-)) solutions in CH(2)Cl(2). The nanoparticle surface coverage (Gamma(NP)) and the stability of the adsorbed nanoparticle film to repeated ferrocene/ferrocenium redox cycling decrease in the order of sulfonate > carboxylate > methyl terminated SAM, with increasing hydrophobicity of X(-) and with increasing alkyl chain length. The results are consistent with the proposal that the strong surface adsorption is jointly associated with the polyfunctional character of the nanoparticles, analogous to entropically driven adsorptions of polymeric ions on charged surfaces, and with lateral, ion-bridged nanoparticle-nanoparticle interactions.

Identification of impurities in ivermectin bulk material by mass spectrometry and NMR.

The identification and characterization of four process impurities in bulk ivermectin and four process impurities in bulk avermectin, using a combination of MS and NMR, are discussed herein. These process impurities were shown to be 24-demethyl H2B1a, 3'-demethyl H2B1a, 3''-demethyl H2B1a and 24a-hydroxy B2a isomer. The impurities were shown to be process impurities and are present in avermectin bulk also.

Development and validation of a stability indicating HPLC method for determination of lisinopril, lisinopril degradation product and parabens in the lisinopril extemporaneous formulation.

The purpose of the research described herein was to develop and validate a stability-indicating HPLC method for lisinopril, lisinopril degradation product (DKP), methyl paraben and propyl paraben in a lisinopril extemporaneous formulation. The method developed in this report is selective for the components listed above, in the presence of the complex and chromatographically rich matrix presented by the Bicitra and Ora-Sweet SF formulation diluents. The method was also shown to have adequate sensitivity with a detection limit of 0.0075 microg/mL (0.03% of lisinopril method concentration). The validation elements investigated showed that the method has acceptable specificity, recovery, linearity, solution stability, and method precision. Acceptable robustness indicates that the assay method remains unaffected by small but deliberate variations, which are described in ICH Q2A and Q2B guidelines.

Characterization of an extemporaneous liquid formulation of lisinopril.

The stability of lisinopril in an extemporaneously prepared suspension stored at or below 25 degrees C for 28 days under ambient light exposure was studied. A formulation of 1-mg/mL oral suspension was prepared from commercially available 20-mg lisinopril tablets, using Bicitra and Ora-Sweet SF as the compounding vehicles to make a final volume of 200 mL. Individual samples, stored in 8-oz amber polyethylene terephthalate bottles, were used for each test performed. All samples were stored at 25 degrees C. Appropriateness of the extemporaneous preparation method was performed by shaking three lots of each suspension for 30, 60, and 90 seconds. To test the robustness and reproducibility of the method, two chemists prepared the suspensions from the same three lots of lisinopril tablets. Chemical and physical stability were established by analyzing duplicate samples at time zero and after one, two, four, and six weeks. The solubility of lisinopril was tested from suspensions stored for four weeks. In-use stability was also examined over four weeks. Photochemical stability was examined by exposing three batches of the suspension to maximum light stress in accordance with the International Conference on Harmonization. Antimicrobial-effectiveness testing was also conducted with freshly prepared suspensions and suspensions stored for six weeks. The preparation method used was appropriate and effective. Lisinopril is fully dissolved in the suspension matrix. Satisfactory chemical, physical, and microbiological results were obtained after the suspensions were stored for six weeks at 25 degrees C and 35% relative humidity. Lisinopril suspensions extemporaneously prepared from tablets are stable for at least four weeks when stored at or below 25 degrees C under ambient light exposure.

Investigation of Electron Transfer by Geobacter sulfurreducens Biofilms by using an Electrochemical Quartz Crystal Microbalance.

Both the short- and long-term electron-transfer processes of electrode-respiring Geobacter sulfurreducens biofilms are demonstrated by using an electrochemical quartz crystal microbalance (QCM). The QCM monitors the frequency shift from the initial resonant frequency (background) in real time, while the current increases, because of biofilm growth. In the short term, the frequency shift is linear with respect to current for the biofilm. In long-term biofilm growth up to the exponential phase, a second linear region of frequency shift with respect to current is observed. In addition to the frequency shift response at constant polarization, the frequency shift response is coupled to cyclic voltammetry experiments. During cyclic voltammetry, a reproducible, negative increase in frequency shift is observed at oxidizing potentials. The results suggest that a QCM can be used in applications in which it is useful to find the most efficient current producer.

Voltammetry and redox charge storage capacity of ferrocene-functionalized silica nanoparticles.

We describe the electrochemistry of 15 nm diameter silica nanoparticles densely functionalized with ferrocene (FcSiO(2)) through siloxane couplings. Each nanoparticle bears approximately 600 Fc sites, as measured by potentiometric titration (590 Fc) and diffusion-controlled voltammetry (585 Fc) and estimated by XPS (630 Fc). The nanoparticle ferrocene coverage amounts to ca. a complete monolayer of ferrocene sites, which react electrochemically without mutual interactions and which are apparently fully accessible for diffusion-controlled electrode reactions. Diffusion-controlled voltammetry of the FcSiO(2) nanoparticles was observed in dilute methanol dispersions and in more concentrated slurry phases formed in methanol/acetonitrile mixtures. Electrochemical studies reveal interesting behavior in the dilute and more concentrated solutions. Because of the large nanoparticle surface area/volume ratio, the ferrocene-coated silica nanoparticles are capable of storing up to 5 x 10(7) C/m(3) of redox charge as dry phases and 6 x 10(5) C/m(3) in the concentrated slurries.